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Specific features of the reaction of anhydrous PtCl4 with 18-crown-6 in anhydrous solvents with different donor and solvating abilities, such as nitromethane, acetonitrile, and 1,2-dichloroethane, under an inert atmosphere are studied. Ionic platinum complexes with oligoethylene glycols or with crown ethers, formed by macroring opening and/or fragmentation under the action of the acidic agent, were isolated. The 1H NMR, IR, and Raman spectra of the complexes were studied. To assess the coordination mode of the crown ether cleavage product with Pt(IV), quantum-chemical calculations at the density functional theory level were carried out.

Compounds of the compositions [2(18-crown-6)⋅6(H2O)⋅2(C2H4Cl2)⋅{Pt2+(C2H4)}⋅(Pt2Cl10)2−], [4(18-crown-6)⋅2(OH3)+⋅2(OH2)⋅2(NH3)⋅(Pt2Cl10)2−], [(dibenzo-18-crown-6)⋅6(H2O)⋅{Pt2+(C2H4)}⋅(Pt2Cl10)2−], and [4(dibenzo-18-crown-6)⋅2(OH3)+⋅2(OH2)⋅2(NH3)⋅Pt2Cl10)2−] were prepared by reactions of H2PtCl6 with 18-crown-6 and dibenzo-18-crown-6.

Under conditions of the phase transfer catalysis, acylation of (thio)phosphorylacetonitriles by (het)aroyl chlorides affords the Z-enol forms of C-acylation products in high yields. Their configurations were studied by IR spectroscopy, dipole moment measurements, and ab initio quantum-chemical calculations [B3LYP/6-31G(d)]. The C=C double bond and the phosphoryl or thiophosphoryl group have an s-cis arrangement. The possibility of strong intramolecular hydrogen bonding in these conformers is the governing factor responsible for the three-dimensional structures of the compounds under investigation. Derivatives of nicotinic acid existing in the individual form as zwitterions are the only exceptions.

2-X-5,6-benzo-1,3,2-dioxaphosphinin-4-ones (X = N = C = O, Cl, NEt2), regardless of their aggregative state, prefer one and the same conformation (flattened sofa); the exocyclic substituent occupies either an axial (N = C = O, NEt2) or an equatorial (Cl) position.

A preparation method was developed for new representatives of halonitroenamines, 1-bromo-1-nitro-2-piperidino(cyclohexylamino)-2-phenylethenes. Both molecules possess E configuration and are of high polarity.

The products of the reactions between potassium hexachloroplatinate {K2PtCl6} and 18-crown-6 or dibenzo-18-crown-6 in acetonitrile were studied. Pure crystalline compounds [2K·2(18-crown-6)· 2CH3CN]2+·[PtCl6]2-·2H2O, [2K·dibenzo-18-crown-6·CH3CN]2+·[PtCl6]2-, and [2K·dibenzo-18-crown-6·CH3CN]2+·[Pt2Cl10]2- were obtained. Physicochemical properties of these compounds were studied, and their near- and far-IR IR spectra and thermogravimetric curves were considered. The composition of the complexes is determined by metal:ligand molar ratio and crown ether nature. It was found that acetonitrile is coordinated via the nitrogen atom.

Under conditions of the phase transfer catalysis, acylation of (thio)phosphorylacetonitriles by (het)aroyl chlorides affords the Z-enol forms of C-acylation products in high yields. Their configurations were studied by IR spectroscopy, dipole moment measurements, and ab initio quantum-chemical calculations [B3LYP/6-31G(d)]. The C=C double bond and the phosphoryl or thiophosphoryl group have an s-cis arrangement. The possibility of strong intramolecular hydrogen bonding in these conformers is the governing factor responsible for the three-dimensional structures of the compounds under investigation. Derivatives of nicotinic acid existing in the individual form as zwitterions are the only exceptions.

1. The reaction of trichloroacetyl isocyanate with acyclic and cyclic 1,3-dienes proceeds by the scheme of 1,2-cyclo-addition with the formation of 2-azetidinone derivatives. 2. The saponification of the adducts makes it possible to obtain previously unknown unsaturatedβ-aminocarboxylic acids.

The reaction of dibenzylphosphinous acid with formic acid esters was studied in the presence of sodium. Here we obtained dibenzylmethylolphosphine oxide and the enol form of the phenylalkoxybenzylphosphorylacetaldehyde.

The spectral characteristics and ionization constants of some five-, seven-, and eight-membered cyclic arylenephosphorous acids were determined, and a conclusion regarding the effect of the size of the ring on the tautomerism of these compounds was made on their basis.